EP0447672A1 - Process of treating waste paper by enzymatic de-inking - Google Patents

Process of treating waste paper by enzymatic de-inking Download PDF

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Publication number
EP0447672A1
EP0447672A1 EP19900125379 EP90125379A EP0447672A1 EP 0447672 A1 EP0447672 A1 EP 0447672A1 EP 19900125379 EP19900125379 EP 19900125379 EP 90125379 A EP90125379 A EP 90125379A EP 0447672 A1 EP0447672 A1 EP 0447672A1
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Prior art keywords
added
reaction solution
reaction
waste paper
minutes
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German (de)
French (fr)
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EP0447672B1 (en
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Hans-Peter Dr. Call
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LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERT
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LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG und ZUM VERTRIEB VON ENZYMEN mbH
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02—Working-up waste paper
    • D21C5/025—De-inking
    • D21C5/027—Chemicals therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the present invention relates to a method for processing waste paper with enzymatic ink removal.
  • waste paper preparation with ink removal is a chain of different sub-processes.
  • the selection of the aggregates to be used and the design of the overall system must always be made in relation to the end product, taking into account the economic aspect of minimizing costs and the technological aspect of optimizing the quality properties of the pulp.
  • the goal of waste paper processing in the deinking process is the quantitative removal of ink particles with minimal loss of those substances that are valuable for the subsequent paper production.
  • Immediately associated with this goal is the desire to free the heterogeneous waste paper input material from all the solid, dissolved or colloidally dissolved substances in such a way that paper production is not adversely affected and the quality of the paper is not reduced. Which Waste paper ingredients that are valuable for waste paper production depend on the quality requirements of the end product.
  • the flotation tube cell was redesigned in 1982 with the aim of reducing energy, improving deinking efficiency and increasing safety. Only the shape of the tubular cell was preserved.
  • the ventilation was changed from mechanical to injector ventilation.
  • the injector works on the Venturi principle self-priming and allows ventilation up to 30%.
  • the foam is discharged automatically without a paddle.
  • Verticel flotation cell which consists of two cylindrical containers of different diameters standing one above the other.
  • the substance is fed tangentially into the lower container via injectors.
  • the material-air suspension flow rises and passes through a partition into the upper cylindrical container, which has a larger diameter.
  • the partition is exceeded, the air bubbles are caught by the foam suction.
  • the substance is drained off tangentially from below and fed to a level vessel.
  • the level vessel keeps the suspension level at a constant distance from the foam suction tube so that no level control is necessary.
  • the object of the present invention is to provide a method for paper preparation by means of enzymatic printing paper removal which does not have the disadvantages of the chemical and enzymatic methods mentioned above.
  • a redox potential in the range from 200 to 500 mV is set while simultaneously adding oxidizing and reducing agents to a solution containing waste paper
  • a lignin-degrading reaction is started by adding lignolytic enzymes
  • c) the reaction is stopped
  • Addition of 60 to 80 l / h Air per 1.51 reaction volume, at 40 ° C, 0.8 to 2.5% consistency and a stirrer speed of 1200 to 1600 rpm is continued in a commercial flotation system for about 10 minutes and d) the reaction with reduced supply and reduced Stirrer speed continues for 60 to 90 minutes.
  • step d) can also be carried out before step c) or can be omitted entirely.
  • copper (II) sulfate, Mn (II) sulfate, Mn (II) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (IV) ammonium nitrate and Ce (III) nitrate can be used as redox mediators.
  • Zinc, antimony and lead salts are also suitable.
  • Phenolic compounds are added to the reaction as enzyme protection agents. Veratryl alcohols are particularly suitable as such.
  • reaction solution In addition to the chemicals mentioned, other substances can also be added to the reaction solution. These include sodium hypochlorite, polysaccharides such as glucans and / or xanthans, detergents, surfactants, fatty acids such as oleic acids, heme compounds such as hemoglobin, and bleaching reagents, e.g. Sodium perborate. Common bleaching agents such as sodium hypochlorite, oxygen, chlorine dioxide, ozone, H2O2 and sodium dithionite can be used to bleach the decolorized paper.
  • bleaching reagents e.g. Sodium perborate.
  • bleaching agents such as sodium hypochlorite, oxygen, chlorine dioxide, ozone, H2O2 and sodium dithionite can be used to bleach the decolorized paper.
  • Lignolytic enzymes such as phenol oxidases, laccases and lignin peroxidases are used as enzymes.
  • This also includes the lignolytic enzymes obtained from the fungus Phanerochaete chrysosporium. However, it does not have to be the special enzymes obtained according to the US patents mentioned. According to the invention, it is neither necessary to use the enzymes in highly purified form nor to use the enzymes obtained from microorganisms by means of specially optimized mutants. Rather, it is sufficient to use the crude enzymes which are commercially available today for the process according to the invention. In addition to the lignolytic enzymes, pectinases and / or hemicellulases can also be used.
  • the great advantage of the method according to the invention is based on the no longer necessary pretreatment before the actual flotation process by means of the flotation chemicals mentioned at the outset, which took up to 90 minutes according to the prior art.
  • the fact that alkalis and similar substances are only added to the process to a small extent means that the process according to the invention is distinguished by its environmentally friendly waste products.
  • the tear length of the treated fabric can be improved by more than 30% at a lignin removal rate of approx. 5-8%.
  • surfactants in the process according to the invention is no longer absolutely necessary.
  • the polysaccharides present in the crude enzyme partially take on the task of foaming the surfactants.
  • these accumulate as amphoteric substances with their hydrophobic molecules on the originally hydrophobic ink particles.
  • the soap components not precipitated by the water hardness-forming ions become active as foaming agents and dispersing agents.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Paper (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Processing Of Solid Wastes (AREA)
  • Paints Or Removers (AREA)
  • Cephalosporin Compounds (AREA)
  • Press Drives And Press Lines (AREA)
  • Ink Jet (AREA)

Abstract

Process for processing waste paper with enzymatic removal of printing ink, in which a) the redox potential of a solution containing waste paper is adjusted to a value in the range of 200 to 500 mV by simultaneous dosing of oxidizing and reducing agents, b) a lignin-decomposing reaction is initiated by addition of lignolytic enzymes, c) the reaction is continued for approximately 10 minutes by adding 60 to 80 litres/hour of air per 1.5 litres of reaction volume at 40 DEG C, 0.8 to 2.5 % substance density and a stirrer speed of 1200 to 1600 rpm in a standard commercial flotation installation, and d) the reaction continues for 60 to 90 minutes with a reduced supply of air and at reduced stirrer speed.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Altpapieraufbereitung mit enzymatischer Druckfarbenentfernung.The present invention relates to a method for processing waste paper with enzymatic ink removal.

In der betrieblichen Praxis ist die Altpapieraufbereitung mit Druckfarbenentfernung (Deinking) eine Verkettung verschiedener Teilprozesse. Dabei haben die Auswahl der einzusetzenden Aggregate und Auslegung des Gesamtsystems immer in Bezug auf das Endprodukt, unter Berücksichtigung des wirtschaftlichen Aspekts der Kostenminimierung und des technologischen Aspekts der Optimierung der Qualitätseigenschaften der Halbstoffe, zu erfolgen. Das Ziel einer Altpapieraufbereitung im Deinking-Prozeß ist die möglichst quantitative Entfernung von Druckfarbenpartikeln bei minimalem Verlust jener Stoffe, die für die anschließende Papierherstellung wertvoll sind. Unmittelbar mit diesem Ziel ist der Wunsch verbunden, den heterogenen Altpapier-Eingangsstoff von all den festen, gelösten oder kolloidalgelösten Substanzen so zu befreien, daß die Papierherstellung nicht störend beeinflußt und die Qualität des Papiers nicht gemindert wird. Welche Altpapierinhaltsstoffe für die Altpapierherstellung wertvoll sind, richtet sich nach den Qualitätsanforderungen des Endprodukts. So sind z.B. Füllstoffe bei Zeitungsdruckpapier in gewissen Grenzen ein wertvoller Bestandteil, bei der Herstellung von Tissue-Papieren dagegen unerwünscht. Demgemäß sind nach dem Stand der Technik eine Vielzahl von Verfahren untersucht und vorgeschlagen worden (Lausch, H.; Ortner, H.: "Über den Einfluß der Druckfarbenzusammensetzung auf den Deinkingprozeß" Wochenbl. f. Papierf. 94 (1966,) Nr. 5, S. 129-136; Berndt, W.: "Druckfarben und Deinken" Wochenbl. f. Papierf. 104 (1976), Nr. 3, 95-98; Forester, W.K.: "Deinking of UV-cured links'' Tappi J. (1987), Nr. 5, 127-130; N.N.: "Deinkbarkeit von Flexodruck-Tageszeitungen" IFRA Special Report 1.3, Darmstadt, Oktober 1987; Putz, H.J.: "Upcyling von Altpapier für den Einsatz in höherwertigen graphischen Papieren durch chemisch-mechanische Aufbereitung (Deinken und Bleichen)" Dissertation, Technische Hochschule Darmstadt, 1987; Weidhass, A.G.: "Erfahrungen mit einer Deinking Anlage zur Erzeugung von Zeitungsdruckpapier'' Wochenbl. f. Papierf. 104 (1976), Nr. 22, 857-865; Lippert, G.V.: "Erfahrungen mit der Deinkinganlage für Zeitungsdruckpapier der Leykam-Mürztaler AG im Werk Bruck"- Wochenbl. f. Papierf. 111 (1983), Nr. 15. 540-542). Alle diese Verfahren arbeiten mit physikalischchemischen Methoden. Ein biologisch oder enzymatisch arbeitendes Verfahren ist aus dem Stand der Technik nicht bekannt.In operational practice, waste paper preparation with ink removal (deinking) is a chain of different sub-processes. The selection of the aggregates to be used and the design of the overall system must always be made in relation to the end product, taking into account the economic aspect of minimizing costs and the technological aspect of optimizing the quality properties of the pulp. The goal of waste paper processing in the deinking process is the quantitative removal of ink particles with minimal loss of those substances that are valuable for the subsequent paper production. Immediately associated with this goal is the desire to free the heterogeneous waste paper input material from all the solid, dissolved or colloidally dissolved substances in such a way that paper production is not adversely affected and the quality of the paper is not reduced. Which Waste paper ingredients that are valuable for waste paper production depend on the quality requirements of the end product. For example, fillers are a valuable ingredient in newsprint, but are undesirable in the manufacture of tissue paper. Accordingly, a large number of processes have been investigated and proposed according to the prior art (Lausch, H .; Ortner, H .: "About the Influence of the Ink Composition on the Deinking Process" Wochenbl. F. Papierf. 94 (1966,) No. 5 , Pp. 129-136; Berndt, W .: "Druckfarben und Deinken" Wochenbl. F. Papierf. 104 (1976), No. 3, 95-98; Forester, WK: "Deinking of UV-cured links '' Tappi J. (1987), No. 5, 127-130; NN: "deinkability of flexographic daily newspapers" IFRA Special Report 1.3, Darmstadt, October 1987; Putz, HJ: "Upcyling of waste paper for use in higher quality graphic papers by chemical means - mechanical processing (deinking and bleaching) "Dissertation, Technische Hochschule Darmstadt, 1987; Weidhass, AG:" Experience with a deinking plant for the production of newsprint paper '' Wochenbl. f. Papierf. 104 (1976), No. 22, 857- 865; Lippert, GV: "Experience with the deinking system for newsprint from Leykam-Muerstaler AG in the Bruck plant" - Wochenbl. F. Paper 111 (1983), No. 15, 540-542). All of these methods work with physicochemical methods. A biologically or enzymatically working method is not known from the prior art.

Ein heute sehr weit verbreitetes Verfahren ist die Flotationstechnik. Anfang der 60-iger Jahre wurde eine rechteckige Flotationszelle mit mechanischer Verteilung der Flotationsluft von Voit entwickelt. Die Suspension gelangt in dieser Zelle zu einem Laufrad, das von einem konzentrisch angeordneten Lochmantel umgeben ist, sich am Boden der Zelle befindet und von oben angetrieben wird. Die Zelle arbeitet selbstansaugend. Das Laufrad sorgt für die Feindispergierung der Luft in der Suspension, für die Druckfarbenpartikel-Farben-Stöße und für die Verteilung des Stoffe über dem Boden der Zelle. Der Gutstoff wird über einen Überlauf abgeführt, der Schaum mit Hilfe eines Paddels ausgetragen.A very widespread process today is the flotation technique. At the beginning of the 1960s, a rectangular flotation cell with mechanical distribution of the flotation air was developed by Voit. The suspension reaches an impeller in this cell, which is surrounded by a concentrically arranged perforated casing, is located at the bottom of the cell and from above is driven. The cell works self-priming. The impeller ensures the fine dispersion of the air in the suspension, the ink particle-color impacts and the distribution of the substance over the bottom of the cell. The accepted material is discharged via an overflow, the foam is removed using a paddle.

Um die Hydrodynamik der Zelle zu verbessern wurde 1978 die Flotations-Rohr-Zelle entwickelt. Art der Belüftung sowie mechanische Feindispergierung der Luft wurden bei diesem Konzept von der geschilderten Flotationszelle übernommen.In 1978 the flotation tube cell was developed to improve the hydrodynamics of the cell. With this concept, the type of ventilation and mechanical fine dispersion of the air were adopted from the flotation cell described.

Mit dem Ziel der Energiereduzierung, Verbesserung des Deinking-Wirkungsgrades und erhöhter Sicherheit wurde die Flotations-Rohr-Zelle 1982 neu konstruiert. Erhalten blieb ausschließlich die Form der Rohrzelle. Bei der Belüftung ging man von der mechanischen auf die Injektorbelüftung über. Der Injektor arbeitet nach dem Venturi-Prinzip selbstansaugend und erlaubt eine Belüftung bis zu 30 %. Der Schaumaustrag erfolgt selbsttätig ohne Paddel.The flotation tube cell was redesigned in 1982 with the aim of reducing energy, improving deinking efficiency and increasing safety. Only the shape of the tubular cell was preserved. The ventilation was changed from mechanical to injector ventilation. The injector works on the Venturi principle self-priming and allows ventilation up to 30%. The foam is discharged automatically without a paddle.

Im Jahre 1984 wurde die Kompakt-Flotationszelle vorgestellt. Für die Flotation in dieser Zelle sind zwei Faktoren von ausschlaggebender Bedeutung: 1) ein geeignetes Belüftungselement vor der Zelle: der Stufendifusor und 2) eine den Trennvorgang begünstigende Hydrodynamik der Zelle. Der belüftete Stoff wird an vier Stellen tangential der runden, stehenden Zelle zugeführt. Im Gegensatz zu allen anderen Flotationszellen erfolgt der Stoffzulauf nur unterhalb der Suspensionsoberfläche. Optimale Durchmischung von Luft und Suspension vorausgesetzt, soll eine sofortige gegenläufige Strömung in der Zelle (Luft mit Druckfarbenpartikeln nach oben und Gutstoff nach unten) das Wiederablösen der Druckfarbenpartikel von den Luftblasen vermeiden.In 1984 the compact flotation cell was introduced. Two factors are of crucial importance for the flotation in this cell: 1) a suitable ventilation element in front of the cell: the step diffuser and 2) a hydrodynamics of the cell which favors the separation process. The aerated fabric is fed tangentially to the round, standing cell at four points. In contrast to all other flotation cells, the material feed takes place only below the suspension surface. Provided the air and suspension are optimally mixed, an immediate counter-current flow in the cell (air with ink particles upwards and accept substance downwards) should prevent the ink particles from detaching again from the air bubbles.

Weiterhin ist eine sogenannte Verticel-Flotationszelle bekannt, welche aus zwei übereinanderstehenden zylindrischen Behältern unterschiedlichen Durchmessers besteht. Der Stoff wird hierbei über Injektoren tangential in den unteren Behälter geleitet. Der Stoff-Luft-Suspensionsstrom steigt auf und gelangt über eine Trennwand in den oberen zylindrischen Behälter, der einen größeren Durchmesser hat. Beim Übersteigen der Trennwand werden die Luftblasen von der Schaumabsaugung erfaßt. Im äußeren Behälter wird der Stoff von unten tangential abgeführt und einem Niveaugefäß zugeleitet. Das Niveaugefäß sorgt für einen konstanten Abstand des Suspensionsspiegels vom Schaumabsaugrohr, so daß keine Niveauregelung notwendig ist.Furthermore, a so-called Verticel flotation cell is known, which consists of two cylindrical containers of different diameters standing one above the other. The substance is fed tangentially into the lower container via injectors. The material-air suspension flow rises and passes through a partition into the upper cylindrical container, which has a larger diameter. When the partition is exceeded, the air bubbles are caught by the foam suction. In the outer container, the substance is drained off tangentially from below and fed to a level vessel. The level vessel keeps the suspension level at a constant distance from the foam suction tube so that no level control is necessary.

Neben den vorgestellten Flotationsverfahren gibt es noch weitere Verfahren. welche hier nicht näher erläutert werden sollen. Gemeinsam ist allen diesen Verfahren, daß sie unter Einsatz von umweltbelastenden Chemikalien arbeiten.In addition to the flotation processes presented, there are other processes. which are not to be explained in more detail here. All these processes have in common that they work using environmentally harmful chemicals.

Aus den US-PS 4 687 745, 4 692 413 und 4 690 895 ist bekannt, daß sich die durch spezielle Mutanten des Pilzes Phanerochaete chrysosporium erzeugten Enzyme für die Entfärbung von zellstoffhaltigem Material eignen, was aber mit einem Deinking-Prozeß nichts zu tun hat. Auch ist ein solches Verfahren zeitintensiv (ca. 12 Stunden). Zudem können die Enzyme nur aus dem speziell gezüchteten Stamm von Phanerochaete chrysosporium gewonnen werden.From US Pat. Nos. 4,687,745, 4,692,413 and 4,690,895 it is known that the enzymes produced by special mutants of the fungus Phanerochaete chrysosporium are suitable for decolorizing cellulose-containing material, but this has nothing to do with a deinking process . Such a procedure is also time-consuming (approx. 12 hours). In addition, the enzymes can only be obtained from the specially cultivated strain of Phanerochaete chrysosporium.

Die vorliegende Erfindung hat sich nunmehr die Aufgabe gestellt, ein Verfahren zum Papieraufbereiten mittels enzymatischen Druckpapierentfernens zur Verfügung zu stellen, welches die oben angeführten Nachteile der chemischen und enzymatischen Verfahren nicht aufweist.The object of the present invention is to provide a method for paper preparation by means of enzymatic printing paper removal which does not have the disadvantages of the chemical and enzymatic methods mentioned above.

Diese Aufgabe wird dadurch gelöst, daß a) unter gleichzeitiger Zudosierung von Oxidations- und Reduktionsmitteln zu einer Altpapier enthaltenden Lösung ein Redoxpotential im Bereich von 200 bis 500 mV eingestellt, b) durch Zugabe von lignolytischen Enzymen eine ligninabbauende Reaktion gestartet und c) die Reaktion unter Zugabe von 60 bis 80 l/Std. Luft pro 1,51 Reaktionsvolumen, bei 40° C, 0,8 bis 2,5 % Stoffdichte und einer Rührergeschwindigkeit von 1200 bis 1600 rpm in handelsüblicher Flotationsanlage für ca. 10 Min. fortgeführt wird und d) die Reaktion unter vermindeter Zufuhr und reduzierter Rührergeschwindigkeit 60 bis 90 Minuten weiterläuft. Hierbei kann Schritt d) auch vor Schritt c) durchgeführt werden oder ganz wegfallen.This object is achieved in that a) a redox potential in the range from 200 to 500 mV is set while simultaneously adding oxidizing and reducing agents to a solution containing waste paper, b) a lignin-degrading reaction is started by adding lignolytic enzymes, and c) the reaction is stopped Addition of 60 to 80 l / h Air per 1.51 reaction volume, at 40 ° C, 0.8 to 2.5% consistency and a stirrer speed of 1200 to 1600 rpm is continued in a commercial flotation system for about 10 minutes and d) the reaction with reduced supply and reduced Stirrer speed continues for 60 to 90 minutes. Here step d) can also be carried out before step c) or can be omitted entirely.

Neu ist die erfindungsgemäße Kombination eines Enzymsystems mit den an sich bekannten Flotationsverfahren. Dadurch wird erreicht, daß anstelle der üblichen, oben geschilderten Flotationschemikalien, wie NaOH, H₂O oder Ölsäure die Druckfarbenentfernung weitgehend durch lignolytische Rohenzyme bewerkstelligt wird. Der eigentliche Prozeß des Entfärbens beruht bei dem erfindungsgemäßen Verfahren wahrscheinlich auf einer Lockerung der Fasern - wie bereits oben erwähnt - durch den Angriff des Enzyms auf das Lignin. Die Wirkung ist ähnlich der Quellwirkung von Natronlauge auf die Faser bei den konventionellen, eingangs erwähnten Entfärbungsverfahren. Es kommt also durch die Lockerung mittels der Enzyme zu einer Loslösung der Druckfarbenteilchen von der Faser. Aufgrund der aufgelockerten Struktur läßt sich im anschließenden Flotationsverfahren die Druckfarbe leicht entfernen, so daß meist nur eine zusätzliche Zudosierung eines Schäumers in geringsten Konzentrationen nötig ist.What is new is the combination of an enzyme system according to the invention with the flotation processes known per se. It is thereby achieved that instead of the usual flotation chemicals described above, such as NaOH, H₂O or oleic acid, the removal of the printing ink is largely accomplished by raw lignolytic enzymes. The actual process of decolorization in the process according to the invention is probably based on a loosening of the fibers - as already mentioned above - by the attack of the enzyme on the lignin. The effect is similar to the swelling effect of sodium hydroxide solution on the fiber in the conventional decolorization processes mentioned at the beginning. As a result of the loosening by means of the enzymes, the ink particles become detached from the fiber. Due to the loosened structure, the printing ink can be easily removed in the subsequent flotation process, so that usually only an additional addition of a foamer in the smallest concentrations is necessary.

Zusätzlich können als Redoxmeditatoren Kupfer(II)sulfat, Mn(II)sulfat, Mn(II)acetat, Fe(II)sulfat, Ti(III)chlorid, Ce(IV)amoniumnitrat und Ce(III)nitrat verwendet werden. Ebenso eignen sich Zink-, Antimon- und Bleisalze.In addition, copper (II) sulfate, Mn (II) sulfate, Mn (II) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (IV) ammonium nitrate and Ce (III) nitrate can be used as redox mediators. Zinc, antimony and lead salts are also suitable.

Phenolische Verbindungen werden als Enzymschutzstoffe der Reaktion zugesetzt. Als solche eignen sich besonders Veratrylalkohole.Phenolic compounds are added to the reaction as enzyme protection agents. Veratryl alcohols are particularly suitable as such.

Neben den genannten Chemikalien können noch weitere Stoffe der Reaktionslösung zugesetzt werden. Hierzu gehören Natriumhypochlorit, Polysaccharide wie Glukane und/oder Xanthane, Detergenzien, Tenside, Fettsäuren wie Ölsäuren, Hämverbindungen wie Hämoglobin, und Bleichreagenzien, z.B. Natriumperborat. Zum Nachbleichen des entfärbten Papiers können gängige Bleichmittel wie Natriumhypochlorit, Sauerstoff, Chlordioxid, Ozon, H₂O₂ und Natriumdithionit eingesetzt werden.In addition to the chemicals mentioned, other substances can also be added to the reaction solution. These include sodium hypochlorite, polysaccharides such as glucans and / or xanthans, detergents, surfactants, fatty acids such as oleic acids, heme compounds such as hemoglobin, and bleaching reagents, e.g. Sodium perborate. Common bleaching agents such as sodium hypochlorite, oxygen, chlorine dioxide, ozone, H₂O₂ and sodium dithionite can be used to bleach the decolorized paper.

Als Enzyme werden lignolytische Enzyme, wie Phenoloxidasen, Laccasen und Ligninperoxidasen eingesetzt. Hierzu zählen auch die aus dem Pilz Phanerochaete chrysosporium gewonnenen lignolytischen Enzyme. Es muß sich aber dabei nicht um die gemäß den erwähnten US-Patentschriften gewonnenen speziellen Enzymen handeln. Es ist erfindungsgemäß weder notwendig, die Enzyme in hochgereinigter Form noch die mittels spezieller optimierter Mutanten von Mikroorganismen gewonnenen Enzyme einzusetzen. Vielmehr reicht es aus, die heute handelsüblichen Rohenzyme für das erfindungsgemäße Verfahren einzusetzen. Zusätzlich zu den lignolytischen Enzymen können auch Pektinasen und/oder Hemicellulasen eingesetzt werden.Lignolytic enzymes such as phenol oxidases, laccases and lignin peroxidases are used as enzymes. This also includes the lignolytic enzymes obtained from the fungus Phanerochaete chrysosporium. However, it does not have to be the special enzymes obtained according to the US patents mentioned. According to the invention, it is neither necessary to use the enzymes in highly purified form nor to use the enzymes obtained from microorganisms by means of specially optimized mutants. Rather, it is sufficient to use the crude enzymes which are commercially available today for the process according to the invention. In addition to the lignolytic enzymes, pectinases and / or hemicellulases can also be used.

Der große Vorteil des erfindungsgemäßen Verfahrens beruht auf der nicht mehr notwendigen Vorbehandlung vor dem eigentlichen Flotationsprozeß mittels eingangs erwähnten Flotationschemikalien, welche nach dem Stand der Technik bis zu 90 Minuten dauerte. Dadurch, daß Laugen und ähnliche Stoffe nur noch in geringem Umfang dem Prozeß zugesetzt werden, zeichnet sich das erfindungsgemäße Verfahren durch seine umweltschonenden Abfallprodukte aus. Darüber hinaus ist es möglich, durch Vorschalten vor oder Nachschalten nach dem eigentlichen Flotationsprozeß eine Entfernung des Lignins aus dem Altpapier zu erreichen und hierdurch die mechanischen Eigenschaften zu verbessern. Z.B. kann die Reißlänge des behandelten Stoffes um mehr als 30 % bei einer Ligninentfernungsrate von ca. 5-8 % verbessert werden.The great advantage of the method according to the invention is based on the no longer necessary pretreatment before the actual flotation process by means of the flotation chemicals mentioned at the outset, which took up to 90 minutes according to the prior art. The fact that alkalis and similar substances are only added to the process to a small extent means that the process according to the invention is distinguished by its environmentally friendly waste products. In addition, it is possible to remove the lignin from the waste paper by connecting upstream or downstream after the actual flotation process and thereby improving the mechanical properties. E.g. the tear length of the treated fabric can be improved by more than 30% at a lignin removal rate of approx. 5-8%.

Daneben bleibt zu erwähnen, daß der Einsatz von Tensiden bei dem erfindungsgemäßen Verfahren nicht mehr unbedingt erforderlich ist. Vermutlich übernehmen die im Rohenzym vorhandenen Polysaccharide teilweise die Aufgabe der Schäumwirkung der Tenside. Diese lagern sich nämlich bei konventionellen Flotationsprozessen als amphotere Stoffe mit ihren hydrophoben Molekülen an die ursprünglich hydrophoben Druckfarbenteilchen an. Durch die Reaktion mit den Härtebildnern des Wassers ist eine Anlagerung an die vorhandenen Luftblasen möglich. Die nicht durch die wasserhärtebildenden Ionen gefällten Seifenbestandteile werden als Schäumer und Dispergiermittel aktiv.It should also be mentioned that the use of surfactants in the process according to the invention is no longer absolutely necessary. Presumably, the polysaccharides present in the crude enzyme partially take on the task of foaming the surfactants. In conventional flotation processes, these accumulate as amphoteric substances with their hydrophobic molecules on the originally hydrophobic ink particles. Through the reaction with the hardness formers of the water, an accumulation on the existing air bubbles is possible. The soap components not precipitated by the water hardness-forming ions become active as foaming agents and dispersing agents.

Im folgenden wird die Erfindung unter Bezugnahme auf ein Beispiel näher erläutert:
12 g atro Stoff (Altpapier/Tageszeitungen) werden in etwa 2 cm x 2 cm große Stücke zerrissen. Daraufhin werden 300ml Wasser mit einer ungefähren Calciumhärte von 2,5 mmol zugegeben und bei ca. 40oC per Hand homogenisiert und daraufhin bei 3000 rpm 5 Minuten im Desintegrator desintegriert. Anschließend wird bei einer Stoffdichte von 3,5 % 2 Minuten bei 3000 rpm erneut desintegriert. Anschließend wird auf 1,5 l mit Wasser von 40°C aufgefüllt und der Stoff in eine 1,5 l Flotationszelle gegeben.
Es werden 0,1 - 1,5 % H₂O₂ auf atro Papier bezogen zugegeben. Ebenso werden ca. 2 x 10⁻⁵ % - 2 x 10⁻³ % VA auf atro Papier bezogen zugegeben. Nach Zugabe von 500 bis 5000 IU lignolytischen Enzymen (1 IU = Umsatz von 1 nmol VA/min. in Veratrylaldehyd) wird der Deink-Flotationsprozeß durch gleichzeitige Zugabe von 60 l Luft/Std. und 1200 rpm Rührerdrehzahl in Gang gesetzt. Gleichzeitig wird über eine eingetauchte Redoxelektrode über eine Pumpensteuerung die Dosierung von H₂O₂ und Natrium-Bisulfit-Lösung so dosiert, daß ein mittleres Redoxpotential von ca. 400 mV eingestellt bleibt. Der Prozeß wird 10 - 15 Minuten bei 40°C fortgeführt und der Schmutzstoff mittels eines Schabers abgeschöpft.The invention is explained in more detail below with reference to an example:
12 g of dry material (waste paper / daily newspapers) are torn into pieces about 2 cm x 2 cm. Then 300 ml of water with an approximate calcium hardness of 2.5 mmol are added and homogenized by hand at approx. 40 o C and then disintegrated at 3000 rpm for 5 minutes in the disintegrator. Then, at a consistency of 3.5%, disintegration is carried out again at 3000 rpm for 2 minutes. It is then made up to 1.5 l with water at 40 ° C. and the substance is placed in a 1.5 l flotation cell.
There are 0.1 - 1.5% H₂O₂ based on dry paper added. Likewise, approx. 2 x 10 2% - 2 x 10⁻³% VA based on dry paper are added. After adding 500 to 5000 IU of lignolytic enzymes (1 IU = conversion of 1 nmol VA / min. In veratryl aldehyde), the deink flotation process is carried out by simultaneously adding 60 l of air / hour. and 1200 rpm stirrer speed started. At the same time, the dosing of H₂O₂ and sodium bisulfite solution is dosed via an immersed redox electrode via a pump control so that an average redox potential of approximately 400 mV remains set. The process is continued for 10-15 minutes at 40 ° C and the pollutant is skimmed off with a scraper.

Claims (27)

Verfahren zur Altpapieraufbereitung mit enzymatischer Druckfarbenentfernung,
dadurch gekennzeichnet, daß a) unter gleichzeitiger Zudosierung von Oxidations- und Reduktionsmitteln zu einer Altpapier enthaltenden Lösung ein Redoxpotential im Bereich von 200 bis 500 mV eingestellt, b) durch Zugabe von lignolytischen Enzymen eine ligninabbauende Reaktion gestartet und c) die Reaktion unter Zugabe von 60 bis 80 l/Std. Luft pro 1,51 Reaktionsvolumen, bei 40°C, 0,8 bis 2,5 % Stoffdichte und einer Rührergeschwindigkeit von 1200 bis 1600 rpm in handelsüblicher Flotationsanlage für ca. 10 Min. fortgeführt wird und d) die Reaktion unter vermindeter Zufuhr und reduzierter Rührergeschwindigkeit 60 bis 90 Minuten weiterläuft. Process for waste paper processing with enzymatic ink removal,
characterized in that a) a redox potential in the range from 200 to 500 mV is set while simultaneously adding oxidizing and reducing agents to a solution containing waste paper, b) a lignin degrading reaction is started by adding lignolytic enzymes and c) the reaction with the addition of 60 to 80 l / h. Air per 1.51 reaction volume, at 40 ° C, 0.8 to 2.5% consistency and a stirrer speed of 1200 to 1600 rpm is continued in a commercial flotation system for about 10 minutes and d) the reaction continues with reduced feed and reduced stirrer speed for 60 to 90 minutes. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, daß Schritt d) vor Schritt c) ausgeführt wird.Method according to claim 1,
characterized in that step d) is carried out before step c). Verfahren nach einem der Ansprüche 1 oder 2,
dadurch gekennzeichnet, daß Schritt d) entfällt.Method according to one of claims 1 or 2,
characterized in that step d) is omitted. Verfahren nach einem der Ansprüche 1 oder 2,
dadurch gekennzeichnet, daß das Redoxpotential im Bereich von 250 bis 450 mV liegt.Method according to one of claims 1 or 2,
characterized in that the redox potential is in the range of 250 to 450 mV. Verfahren nach einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet, daß als Oxidationsmittel H₂O₂, O₂ oder Ozon eingesetzt wird.Method according to one of claims 1 to 4,
characterized in that H₂O₂, O₂ or ozone is used as the oxidizing agent. Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet, daß als Reduktionsmittel Ascorbinsäure, Dithionit oder Natrium-Bisulfit eingesetzt werden.Method according to one of claims 1 to 5,
characterized in that ascorbic acid, dithionite or sodium bisulfite are used as reducing agents. Verfahren nach Anspruch 6,
dadurch gekennzeichnet, daß Kupfer(II)sulfat auch Mn(II)sulfat, Mn(III)acetat, Fe(II)sulfat, Ti(III)chlorid, Ce(III)nitrat und/oder Ce(IV) amoniumnitrat der Reaktionslösung zugesetzt werden.Method according to claim 6,
characterized in that copper (II) sulfate also Mn (II) sulfate, Mn (III) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (III) nitrate and / or Ce (IV) ammonium nitrate are added to the reaction solution will. Verfahren nach Anspruch 7,
dadurch gekennzeichnet, daß Zink, Antimon- und Bleisalze der Reaktionslösung zugesetzt werden.Method according to claim 7,
characterized in that zinc, antimony and lead salts are added to the reaction solution. Verfahren nach einem der Ansprüche 1 bis 8,
dadurch gekennzeichnet, daß phenolische Verbindungen der Reaktionslösung zugesetzt werden.Method according to one of claims 1 to 8,
characterized in that phenolic compounds are added to the reaction solution. Verfahren nach Anspruch 9,
dadurch gekennzeichnet, daß als phenolische Verbindung Veratrylalkohol verwendet wird.Method according to claim 9,
characterized in that veratryl alcohol is used as the phenolic compound. Verfahren nach einem der Ansprüche 1 bis 10,
dadurch gekennzeichnet, daß als lignolytische Enzyme Phenoloxidasen, Laccasen und Peroxidasen eingesetzt werden.Method according to one of claims 1 to 10,
characterized in that phenol oxidases, laccases and peroxidases are used as lignolytic enzymes. Verfahren nach einem der Ansprüche 1 bis 11,
dadurch gekennzeichnet, daß zusätzlich zu den lignolytischen Enzymen Pektinasen und/oder Hemicellulasen eingesetzt werden.Method according to one of claims 1 to 11,
characterized in that pectinases and / or hemicellulases are used in addition to the lignolytic enzymes. Verfahren nach einem der Ansprüche 1 bis 12,
dadurch gekennzeichnet, daß nur die prosthetischen Gruppen der lignolytischen Enzyme eingesetzt werden.Method according to one of claims 1 to 12,
characterized in that only the prosthetic groups of the lignolytic enzymes are used. Verfahren nach einem der Ansprüche 1 bis 13,
dadurch gekennzeichnet, daß der pH-Wert zwischen 2 und 5 liegt.Method according to one of claims 1 to 13,
characterized in that the pH is between 2 and 5. Verfahren nach einem der Ansprüche 1 bis 14,
dadurch gekennzeichnet, daß pH-Wert 3 beträgt.Method according to one of claims 1 to 14,
characterized in that pH is 3. Verfahren nach einem der Ansprüche 1 bis 15,
dadurch gekennzeichnet, daß Natriumhypochlorit der Reaktionslösung zugesetzt wird.Method according to one of claims 1 to 15,
characterized in that sodium hypochlorite is added to the reaction solution. Verfahren nach einem der Ansprüche 1 bis 16,
dadurch gekennzeichnet, daß der Reaktionslösung Komplexbildner zugesetzt werden.Method according to one of claims 1 to 16,
characterized in that complexing agents are added to the reaction solution. Verfahren nach Anspruch 17,
dadurch gekennzeichnet, daß als Komplexbildner Ethylendiamin-tetraessigsäure (EDTA) oder Diethylentriamin-pentaessigsäure (DTPA) zugesetzt werden.The method of claim 17
characterized in that ethylenediamine-tetraacetic acid (EDTA) or diethylenetriamine-pentaacetic acid (DTPA) are added as complexing agents. Verfahren nach einem der Ansprüche 1 bis 18,
dadurch gekennzeichnet, daß der Reaktionslösung Polysaccharide zugesetzt werden.Method according to one of claims 1 to 18,
characterized in that polysaccharides are added to the reaction solution. Verfahren nach Anspruch 19,
dadurch gekennzeichnet, daß als Polysaccharide Glukane oder Xanthan eingesetzt werden.Method according to claim 19,
characterized in that glucans or xanthan are used as polysaccharides. Verfahren nach einem der Ansprüche 1 bis 20,
dadurch gekennzeichnet, daß der Reaktionslösung Detergenzien zugesetzt werden.Method according to one of claims 1 to 20,
characterized in that detergents are added to the reaction solution. Verfahren nach einem der Ansprüche 1 bis 21,
dadurch gekennzeichnet, daß der Reaktionslösung Tenside zugesetzt werden.Method according to one of claims 1 to 21,
characterized in that surfactants are added to the reaction solution. Verfahren nach einem der Ansprüche 1 bis 22,
dadurch gekennzeichnet, daß Fettsäuren der Reaktionslösung zugesetzt werden.Method according to one of claims 1 to 22,
characterized in that fatty acids are added to the reaction solution. Verfahren nach Anspruch 23,
dadurch gekennzeichnet, daß als Fettsäure Ölsäure eingesetzt wird.The method of claim 23
characterized in that oleic acid is used as the fatty acid. Verfahren nach einem der Ansprüche 1 bis 24,
dadurch gekennzeichnet, daß Hämverbindungen der Reaktionslösung zugesetzt werden.Method according to one of claims 1 to 24,
characterized in that heme compounds are added to the reaction solution. Verfahren nach Anspruch 25,
dadurch gekennzeichnet, daß als Hämverbindung Hämoglobin eingesetzt wird.A method according to claim 25,
characterized in that hemoglobin is used as the heme compound. Verfahren nach einem der Ansprüche 1 bis 26,
dadurch gekennzeichnet, daß Perborat der Reaktionslösung zugesetzt wird.Method according to one of claims 1 to 26,
characterized in that perborate is added to the reaction solution.
EP19900125379 1990-03-20 1990-12-22 Process of treating waste paper by enzymatic de-inking Expired - Lifetime EP0447672B1 (en)

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DE19904008894 DE4008894A1 (en) 1990-03-20 1990-03-20 METHOD FOR RECYCLING PAPER WITH ENZYMATIC PRINT INK REMOVAL

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US5370770A (en) * 1992-11-09 1994-12-06 The Mead Corporation Method for deinking printed waste paper using soybean peroxidase
WO1997046753A1 (en) * 1996-06-03 1997-12-11 Kao Corporation Deinking process
EP1046744A1 (en) * 1999-03-22 2000-10-25 Kalkfabrik Netstal AG Process for removing ink from recycled paper
EP1568384A1 (en) * 2004-02-18 2005-08-31 Sappi Austria Produktions-GmbH & Co. KG. Process for stabilizing germinative fluid media

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US6228128B1 (en) 1997-11-10 2001-05-08 Charlotte Johansen Antimicrobial activity of laccases
KR20160088301A (en) * 2013-11-18 2016-07-25 엔지매틱 데인킹 테크놀로지즈, 엘엘씨 Enzymatic treatment of virgin fiber and recycled paper to reduce residual mineral oil levels for paper production

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US5370770A (en) * 1992-11-09 1994-12-06 The Mead Corporation Method for deinking printed waste paper using soybean peroxidase
WO1997046753A1 (en) * 1996-06-03 1997-12-11 Kao Corporation Deinking process
US6103056A (en) * 1996-06-03 2000-08-15 Kao Corporation Method for controlling deinking flotation using interfacial potential of ink particles and pulp
CN1077632C (en) * 1996-06-03 2002-01-09 花王株式会社 Deinking process
EP1046744A1 (en) * 1999-03-22 2000-10-25 Kalkfabrik Netstal AG Process for removing ink from recycled paper
EP1568384A1 (en) * 2004-02-18 2005-08-31 Sappi Austria Produktions-GmbH & Co. KG. Process for stabilizing germinative fluid media

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NO180725B (en) 1997-02-24
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HUT64118A (en) 1993-11-29
AU652358B2 (en) 1994-08-25
CA2078346A1 (en) 1991-09-21
ES2072964T3 (en) 1995-08-01
AU7543091A (en) 1991-10-21
NO923623D0 (en) 1992-09-17
FI924168A0 (en) 1992-09-17
NO180725C (en) 1997-06-04
WO1991014820A1 (en) 1991-10-03
JPH05506275A (en) 1993-09-16

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